Photographic element protected against action of ultraviolet radiation



limited States Fatefit N. Y., a corporation of New J ersey No Drawing. Application October 31, 1952, Serial No. 318,096

13 Claims. (c1. 95-2) This invention relates to a method of protecting multilayer photographic elements against the action of ultraviolet radiation and to multilayer elements containing ultraviolet filtering materials.

It is known that color photographs on multilayer photographic material, particularly where the dye images are formed in sensitive emulsion layers by color development, are susceptible to fading and discoloration by the action of ultraviolet radiation, to which the photographs are subjected during viewing. It is also known that the residual couplers contained in the emulsion layers after formation of the picture images in certain processes, are attacked by ultraviolet radiation and form astain which is undesirable in the finished photograph. The action of ultraviolet radiation on finished color photographs is particularly noticeable in positive prints on paper or other opaque supports since this type of print is frequently viewed in daylight where there is a high content of ultra violet radiation. I

It is also known that color photographs, especially where the dye images are formed- 'by color development, can be protected from the fading and discoloration caused by ultraviolet light by applying to the finishedcolor pho tograph a layer of gelatin or other colloidal material having therein an ultraviolet absorbing material. A process of this type in which aesculin, quinine, primuline', disalicylbenzidide, etc., are used as ultraviolet absorbing materials in a gelatin overcoating layer is described in Britist Patent 555,929. Processes of this type have the objection that the ultraviolet filtering material must be applied from colloidal solution, e. g. gelatin, and an application of this character requires coatingmachinery and necessitates an additional coating operation after the processing of the color print is finished.

It is likewise known that color photographs, especially where the dye images are formed by color development, can be protected from the fading and discoloration caused by ultraviolet radiation byapplyingto the finished color photograph a layer ofgelatin or other colloidal material having therein a cyanine dye, such as 3,3-di alkyloxacyan'ine halides, 3,3-dialkyldibenzoxacyanine halides, and 3,3'-dialkylthiazolocyanine halides; These cyanine dyes have the desirable property of absorbing ultraviolet light, However, many of them have the seriousdisadvantage of being unstable to prolonged exposure to light. A method of using these cyanine dyesin ultraviolet filters for color materials, is described in Richardson U. S. Patent 2,160,907, issued June 6, 1939.

In the copending application Serial No. 91,422, filed May 4, 1949 (now U. S. Patent 2,632,701, issued March 4, 1953), of I. F. Salminen and C. F. H. Allen, there is described a method of rendering color photographic materials stable against the deteriorating efiects of light, comprising bathing the photographic material in an aqueous solution of various-sulfonic :acid salt compounds. While the method described in the Salminen and Allen application provides many advantages not heretofore obtainable, the method of the Salminen and Allen application does not provide a ready means of incor porating sufficiently large quantities of ultraviolet absorber in the photographic element to secure protection for prolonged periods of time, such as are required for color print materials, for example.

it is, therefore, an object of the present invention to provide a simple method for protecting finished, multilayer photographic materials against the action of ultraviolet radiation. A further object is to provide finished,- multilayer color materials, such as color print materials, in which the color image is not appreciably subject to fading or discoloration by the action of ultraviolet radiation. Other objects will become apparent from a consideration of the following description of our invention.

While the ultraviolet absorbing agents, such as those described in the Richardson Patent 2,160,907 mentioned above, are quite useful for short periods of time, they fail in providing prolonged protection, clue to actual deterioration of the ultraviolet absorbing agent itself upon prolonged exposure to light. We have found that the valuable ultraviolet absorbing properties of ultraviolet absorbing agents (such as those shown in the Richardson patent, for example) which undergo decomposition upon exposure to ultraviolet radiation, can be protected through the use of other ultraviolet absorbing agents (such as those described in Salniinen and Allen application 91,422, for example) mentioned above. The combination of ultraviolet absorbing agents employed in our invention provide prolonged and efiicient protection which has not heretofore been obtainable, the elfect realized being more than a mere additive one;

According to our invention, we accomplish the above objects by applying to a multilayer photographic element an aqueous, non-colloidal solution of at least one watersoluble organic compound which absorbs ultraviolet radiation of wavelengths between about 300 and 400 millimicrons, but transmits light of wavelength longer than 400 millimicrons. The multilayer photographic elements which are treated according to our invention comprise a support having thereon a plurality (e. g. 2 to 3) of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing at least one (e. g. 1 to 3) ultraviolet absorbing compound which absorbs wavelengths of radiation between about 300 and 400 millimicrons (but transmits light of wavelength longer than 400 millimicrons). The ultraviolet absorbing compound in the photographic element is diif erent chemically from that employed in the bathing solution. The combination of dyes exhibits an effect not shared by the compounds individually. The particular combinations of ultraviolet absorbing compounds can be varied, depending on the particular effect desired, although the ultraviolet absorbing compound in the bathing solution must be water-soluble. The ultraviolet absorbing compound in the photographic element may, or may not, be water-soluble, although in the former instance, it" is convenient to employ am'ordant (e. g. polyvinylpyridine methyl p-toluenesulfona'te, etc.) in conjunction with the dye. The reason for the mutual stabilizing elfe'c't' of the ultraviolet compounds is not readily understood, although the effect is not merely an additive one, asrnentioned above.

The following comp'ounds'are illustrative of those'which can advantageously be employed in the photographic element (before treatment with bathing solution):

wherein R and R1 each represent an alkyl group, such as methyl, ethyl, n-propyl, n-lauryl, etc., R2 represents a hydrogen atom, an alkyl group (such as methyl, ethyl, n-propyl, isopropyl, etc., for example), or an aryl group (such as phenyl, o-, m-, and p-tolyl, m-, and p-chlorophenyl, etc., for example), R3, R4, and Rs each represents an aryl group (such as phenyl, o-, m-, and p-tolyl,

o-, m-, and p-anisyl, p-isopropylphenyl, 0-, m-, and p-hydroxyphenyl, 0-, m-, and p-carboxyphenyl, 0-, m-, and pasulfophenyl, etc., for example), R5 represents an alkyl group (such as methyl, ethyl, n-propyl, isopropyl, etc., for example) or an alkoxyl group (such as methoxyl, ethoxyl, etc., for example), Q represents a divalent, nonmetallic atom (e. g. oxygen, sulfur, etc., for example) or radical (e. g. imino, phenylimino, etc., for example), X represents an anion, such as chloride, bromide, iodide, perchlorate, thiocyanate, etc., Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, e. g. those of the benzoxazole series, such as benzoxazole, S-methylbenzoxazole, 5-phenylbenzoxazole, 6-ethoxybenzoxazole, etc., those of the thiazole series, such as thiazole, 4,5-diphenylthiazole, 4-phenylthiazole, 5phenylthiazole, etc., those of the thiazoline series, such as thiazoline, 4phenylthiazoline, etc., those of the benzothiazole series, such as benzothiazole, S-methylbenzothiazole, S-phenylberrzothiazole, etc., and D represents the non-metallic atoms necessary to com plete a fluoranthene nucleus. The gelatin layer containing at least one of the above ultraviolet absorbing compounds, for example, can be the outermost layer of the photographic element, or such layer can be an interlayer, lying between two photographic emulsion layers, one of which is subject to image degradation due to fading of the coupled-dye image. When the gelatin layer containing one of the ultraviolet absorbing compoundsselected from those represented by Formulas I-VIII above is used as an interlayer, its position in the photographic element will depend on which particular emulsion layer containing a coupled-dye image is subject to fading.

In addition to the compounds of Formulas I-Vlll above other ultraviolet compounds which can be used, for example, comprise fluoranthene, 3,8-dibromofiuoranthene, fluoranthene disulfonic acid, butyl 7,*10-diphenylfluoranthene-8,9-dicarboxylate, butyl 7,10-diphenylfluoranthene-9-carboxylate, methyl 7,lO-diphenylfiuoranthene dicarboxylate, 7,8,10 triphenylfluoranthene, 7,10 diphenyl 8 acetofluoranthene, 7,10 diphenylfiuoram thene-S-carboxyisopropylamide, 7,10-diethyl8,9-dihydrofiuoranthene dicarboxylic acid, 7,10-diphenyl-8-aceto- 9-hexylfiuoranthene, [1-n-cetyl-2,S-dimethylpyrrole (3 [3-ethylbenzoxazole (2)] dimethinecyanine chloride, etc. Certain of the above compounds have been previously described in the literature and their method of preparation is known. For a discussion of certain of the above compounds, and others of a similar structure which can be used in our invention, see Synthesis of Fluoranthene Derivatives, Jour. Organic Chem., vol. 17 (1952), p. 845. Other compounds having ultraviolet absorbing properties, which can be used in a manner similar to that of the compounds of Formulas I-VIII, include those described in U. S. Patent 2,112,139, issued March 22, 1938; for example, 1-acetylmethylene-Z-methylbenzothiazoline, 1 methyl 2 propionylmethylene fi naphthothiazoline, 1-trichloroacetylmethylene-2-ethylbenzothiazoline, Z-ethyl-1lauroylmethylenebenzoth'iazoline, etc.

Typical ultraviolet absorbing compounds represented by Formula I above comprise, for example 3,3'-diethyloxacyanine iodide, 3,3-di-n-lauryloxacyanine perchlorate, 3-ethyl-3-n-lauryloxathiazolinocyanine iodide, 3-met'hyl- 3,4-diphenylthiazolinothiazolocyan ine perchlorate, 3,3- diethyl 5,5 diphenyloxacyanine chloride, 3 carboxymethyl-3-ethylthiacyanine iodide, 3,3-diethylthiacyaninep-toluenesulfonate, etc. Typical ultraviolet absorbing compounds selected from those represented by Formula III above comprise, for example, 7,10-diethyl-8,9-dihydrofluoranthene dicarboxylic anhydride, 7,10-diphenyl- 8,9-dihydrofluoranthene dicarboxylic anhydride, etc. Typical ultraviolet absorbing compounds represented by Formula VI above comprise, for example, 5-benzal-2- phenylimino-4-thiazolidone, 5-benzal-3-ethyl-2-phenylimino 4 thiazolidone, 5 anisal 3 phenyl 2 phenylimino-4-thiazolidone, 5-benZal-2,4-dithiothiazoledione, 5- o-chlorobenzal 2,4 dithiothiazoledione, 5 o methoxybenzal-2,4-dithiothiazoledione, S-p-rnethyl enzal-2,4- dithiothiazoledione, 5 o-hydroxybenzal 3 phenyl 7.- phenylimino-4-thiazolidone, 3phenyl-2-phenylimino-5-osulfobenzal-4-thiazolidone, 5o-carboxybcnzal-3-phenyl- 2-phenylimino-4-thiazolidone, 5-cumal-3-phenyl-2-phenylimino-4-thiazolidone, etc. Compounds represented by Formula VI are described in Sawdey application Serial No. 317,864, filed on even date herewith.

Typical ultraviolet absorbing compounds represented by Formula VII above, comprise, for example, 9-ben2alfluorene, 9-p-anisalfluorene, etc. For general method of preparation, see Thiele-Berichte, vol. 33, page 852. Photographic emulsions containing such agents are described in Sawdey application Serial No. 317,865, filed on even date herewith, now U. S. Patent 2,685,512, issued August 3, 1954.

Typical ultraviolet absorbing compounds represented by Formula VIII above, comprise for example, 4-benzoyl 2 methylresorcinol, 4 o carboxybcnzoyl 2- methylresorcinol, 4 p sulfobenzoyl 2 methylresorc'inol, 4 [3 (3 chlorosulfonylbenzamido)benzoyll 6- n-hexylresorcinol, etc. Such compounds can advantageously be prepared as described in application Serial art sts No. 317,904, filed on even date herewith, now U. S. Patent 2,719,086, issued September 27, 1955. The compounds selected from those represented by Formulas I to VIII above can be incorporated in the photographic element (usually prior to exposure and processing) in the form of their solutions, or where sufiiciently soluble, by means of a gelatin dispersion. This process has been fully described in the Richardson patent mentioned above.

The water-soluble organic compounds, which are employed for treating the photographic element containing different ultraviolet absorbing compounds selected from those of Formulas I-VIII in one of the gelatin layers, comprise compounds selected from those represented by the following formulas, for example:

Di-(2'-hydroiy 3'-methylbenzoylj benzidide sodium sulfonate come oNH- -on=o'n- -NH0 0 can,

O Na SOgNa 4,4'-di- (phenylcarbamldo) -stilbene-2,2' disulfoi1ic acid (Na salt) Hoot coon X NaO s some 7 03 EH l I N/ b-NH- CH=GHNH-C/ \N EN NH C O:Na OsNB- I, A 'H on a water-soluble sulfonic acid salt of a compound selected from those having the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, such as phenyl, p-hydroxyphenyl, p-tolyl, etc., It represents a positive integer of from 1 to 3, and Y represents a member selected from the group consisting of a s-triazinyl and an acyl group of a mom onuclear aromatic carboxylic acid, such as benzoyl, and its hydroxyl, alkyl, alkoxyl, etc., derivatives, the watersoluble cyanine dyes selected from those of Formula 1 above, the water-soluble compounds of Formulas VI-- VIII (e. g. those compounds wherein R3,- R4 or Rs represents an aryl group containing a solubilizing group, such as hydroxyl, carboxyl, sulfo, etc.).

The following compounds are illustrative of the watersoluble compounds of Formula XII whose aqueous solutions are useful for treating the photographic elements described above according to our invention.

D'isalicylb'enzidide sodium suli'onate S OZNa OsN Disalicyltoluidide sodium sulfonate a O 0 H3 0 C H: 0 H

Disalicyl-di oanisidide sodium sulfonate 4,4-di- 3" ,5 -dihydroxy-s-triazlnylnmino) -stilbene-2,2'- disulfonlc acid (Na salt) 8 OCH; OCH:

iO Na AO Na Di-(3-sulfobenzoyl)-o-dianisidide sodium salt Cs-GNE MW QzNSt SOaNQ Di-(3'-suliobenzoyl)benzidide sodium salt The above water-soluble ultraviolet absorbing materials have a high ultraviolet absorption in the regions between about 300 and 400 millimicrons, but relatively little absorption in the visible region of the spectrum at wavelength longer than 400 millimicrons. Advantageously, we can apply aqueous solutions of the above water-soluble ultraviolet absorbing materials to a multilayer photographic element, such as those described in U. S. Patent 2,304,940 issued December 15, 1942, U. S. Patent 2,322,027, issued June 15, 1943, or U. S. Patent 2,160,907, issued June 6, 1939, by bathing or coating from a simple aqueous solution after the multilayer ele menthas been developed and fixed. The solution of the ultraviolet absorber can be used as the final stage of the processing of the material described in the U. S. Patents 2,160,907; 2,304,940; or 2,322,027, that is, after the final wash but before drying. However, if the multilayer elementhas been Washed and dried, the ultraviolet absorber may be applied after drying and the photograph rinsedand dried.- It is to be understood that by reference to the photographic elements described in U. S. Patents 2,160,907, 2,304,940 and 2,322,027, we refer to multilayer color materials containing in addition to the emulsion layers containing the dye couplers, a gelatin layer containing at least one ultraviolet absorbing compound, such as one of those selected from Formulas I to VIII above. By bathing the photographic multilayer materials containing a gelatin layer containing at least Di ('2'-hydroxyA'-methylbenzoyl)-benzidide sodium snlfouate one ultraviolet absorbing compound, such as one of those selected from Formulas I to VIII above with an aqueous solution containing at least one, different, water-soluble organic compound, such as those selected from Formulas IX to XII, we obtain results which cannot be obtained through the use of either class of ultraviolet absorbing compound alone. That is, an effect similar to a synergistic effect is obtained.

The following example illustrates a method of applying the water-soluble organic compound, such as those selected from Formulas IX to XII to the multilayer photo graphic element containing at least one, different ultraviolet absorbing compound, such as those selected from Formulas I to VIII.

A multilayer photographic element containing a gelatin layer having dispersed therein an oxacyanine dye (such as described in 2,160,907), and if desired another ultraviolet absorbing compound such as fluoranthene, 7,10- diethyl-8,9-dihydrofluoranthene dicarboxylic anhydride, acetylcoumarin, 3-acetylacenaphthene, methyl N-n-laurylanthanilate, or the like, is processed according to the method described in U. S. Patent 2,304,940 or 2,322,027. After the final washing step, the photographic element is treated in the following solution for ten minutes:

Disalicylbenzidide sodium sulfonate grams Sodium hydroxide do 0.6 Hydrochloric acid (1%) cc 5.5

Water to 1 liter.

Grams Citric acid monohydrate Borax 16 Water to 1 liter.

In some cases this prevents excessive yellowing of the residual magenta coupler in the multilayer element on storage of the finished print under high humidity conditions. The aforesaid buffer treatment has nothing to do with the absorption of the ultraviolet absorbers.

The ultraviolet absorbing compound applied to the photographic element by means of an aqueous solution is usually dispersed in varying degrees of concentration throughout the entire photographic element, however, there is generally a higher concentration in the gelatin overcoat layer than in the other layers. When the ultraviolet absorbing compounds, such as those represented hy Formulas I to VIlI, are present in the gelatin overcoat layer rather than in a gelatin interlayer, the water-soluble organic compound, such as those selected from Formulas IX to XII will be present primarily in the same layer. When the ultraviolet absorbing compounds, such as those of Formulas I to VIII are present in a gelatin interlayer, the water-soluble compounds, such as those of Formulas IX to XII will be present in one of the other layers, primarily the gelatin overcoat layer.

In order to improve the retention of the water-soluble compounds, such as those of Formulas IX to XII, a mordant for these compounds can be employed in the gelatin layer. Polyvinylpyridine methyl p-toluenesulfonate, phenol-formaldehyde ion exchange resins, etc., have proven particularly useful as a mordant for the various water-soluble compounds of Formulas IX to XII. Such mordants bind the water-soluble absorber more firmly to the gelatin layer and permit a washing operation after application of the absorber. By use of this expedient, the absorber may be introduced at some stage of the process before the final washing, thus obviating the necessity for the aforesaid butfer treatment mentioned above. Styrene-maleamic acid resins (U. S. Patent 2,313,565) have been found to be useful mordants for certain ultraviolet absorbing compounds, such as the cyanine dyes of Formula I. See Fierke application Serial No. 317,896, filed on even date herewith, now U. S. Patent 2,691,579, issued October 12, 1954.

The above enumerated compounds (Formulas I-XII) are representative of those which can be employed in our invention. Other ultraviolet absorbing compounds can be used to advantage, for example, compounds of Formula VHI where R5 is a hydrogen atom and R5 is an aryl group containing a solubilizing group (e. g. hydroxyl, carboxyl, sulfo, etc.) can advantageously be employed in the after bath treatment. The optimum combinations of ultraviolet absorbers can be determined in accordance with the method described in the above example. The advantages of our invention are especially marked when the ultraviolet absorbing compounds present in the processed photographic element (before treating with the water-soluble ultraviolet absorbing compound) provide protection against ultraviolet radiation but undergo decomposition due to absorption of the ultraviolet radiation. The presence of the water-soluble ultraviolet absorbing compound prevents this unwanted effect.

The following examples describe the preparation of various ultraviolet absorbing compounds mentioned above.

Example 1.--Methyl Nn-laurylanthranilate -(OH2)1iCH3 A mixture of 15 g. of methyl anthranilate (Eastman Organic Chemical 159), 25 g. of n-lauryl bromide (Eastman Organic Chemical 896), and 7.6 g. of anhydrous potassium carbonate was heated at ISO-190 C. for 18 hours. The cooled mixture was poured into 40 cc. of water, the oil separated and the aqueous layer extracted twice with 10 cc. portions of ether. The oil and extracts were combined, the ether was distilled, and the residue fractionated in vacuo. The first fraction, 6 g., B. P. C./ 10 mm., consisted mainly of unchanged methyl anthranilate; the second 7.4 g. (57%), B. P. 238-253 C./ 10 mm., was a pale yellow liquid which solidified to a nearly colorless solid. This was chiefly methyl N-laurylanthranilate and was used without further purification. The residue, of which about 5 g. distilled at 265-300" C./4 mm., was a mixture of the monoand di-lauryl derivatives.

The methyl N-lauryl-anthranilate can be crystallized, is desired, from an acetone-methanol mixture by cooling the solution in ice. It then melts at 3940 C.

Example 2.--Disalicylbenzidide sodium sulfonate SO NS. S O Ntt A solution of 40 g. of benzidine, 10 g. of phenyl salicylate and 500 g. of a-chloronaphthalene was heated in a 1-liter flask attached to a 12-inch Vigreux column so that the phenol distilled (180200 C.). When no more phenol distilled, the reaction mixture was heated strongly until the temperature of the distilling vapours was between 235-240" C., at which point the reaction was considered to be complete. On cooling to room temperature, the product separated. It was collected by filtration and washed with dioxane and then acetone. The

gara es yield of light gray product was 88.5 g. (98%); M. P. 320-324 C. i

8.0 g. of finely pulverized disalicylbenzidide were added to 48 ml. of concentrated sulfuric acid, and the reaction mixture was maintained at an inside temperature of 88- 93 C. for 3.5 hours. It appears as a clear dark brown solution at this point. It was poured with good stirring into 240 ml. of 10% potassium chloride, using Dry Ice as an internal coolant. After standing for one hour to allow for coagulation, the product was collected by filtration. The filter cake was boiled with 1 liter of methanol and again filtered. The crude sulfonic acid thus obtained was taken up in 60 ml. of 10% sodium carbonate solution and decolorized twice, using 1.5-2.0 g. portions of decolorizing carbon, after which 6 g. of sodium chloride were added to the boiling solution with good stirring. The stirring was continued while cooling to room temperature and the mixture was then allowed to stand overnight. The crystalline, white product was collected by filtration and washed with methanol. The yield was 3 g. The filtrate was heated to boiling and 10 g. of sodium chloride were added with vigorous stirring and treated as before. After filtering and drying 6.6 g. of product were obtained. The combined yield was 9.6 g. (80% of the theory of 11.9 g.).

Benzidine (4.6 g.; 0.025 mole) was suspended in 150 ml. of acetic acid, and 5 g. of anhydrous sodium acetate was added. Then 13 g. of m chlorosulfonylbenzoyl chloride was added all at once with good stirring. An immediate precipitate was formed. Stirring was continued for one and a half hours. The yellow precipitate was filtered and dried at 80 C. overnight. Yield 17 g.; theory 14.1 g. p

The above sulfonyl chloride (5.3 g.) was dissolved in 330 ml. of water containing 5.0 ml. of fifty percent caustic at 100 C. After treating with decolorizing carbon, the sodium salt was salted out in the usual manner. Yield 3.5 g.

Example 4.'-7,10-diethyl-8,9 dihydrofluoranthenedicarbo'xylic anhydride 36 parts (0.3 mol) of acenaphthenequinone, 50 ml. of di-n-propyl ketone and 300 ml. of methanol were rapidly stirred While 50 ml. of 20 percent methanolic potassium hydroxide were slowly added. Reaction began immediately, the acenaphthenequinone went into solution and 2,5 diethyl-3,4-(l,8-naphthylene)cyclopentadienone (as carbinol) separated as white needles. The reaction mixture was allowed to stand for 4 hours at room temperature, 300 ml. of water were added, and the crystalline product filtered and dried. The yield was 41.5 grams (75%) and the carbinol melted at 154-156" C. This crude product (carbinol) was boiled with 93 ml. of glacial acetic acid for 15 minutes. The carbinol went into solution and, on cooling, 2,5-diethyl-3,4-(1',8'-naphthylene)- cyclopentadienone in dimeric form was obtained, M. P. 184186 C. It weighed 35 grams.

A solution of 3 parts of the dimer of 2,5-diethyl-3,4- (l,8'-naphthylene)cyclopentadienone obtained as described above and 1.5 parts of maleic anhydride in 30 parts of benzene was heated on a steam bath. A vigorous reaction occurred at 70 C. After standing for 5 minutes 10 the solution was refluxed for 10 minutes, cooled, and the 7,10 diethyl-S,9-dihydrofluoranthenecarboxylic anhydride collected on a filter. It was bright yellow, M. P. 184 0., yield 83%.

The sodium salt of 4,4'-disulfo p-terphenyl can be prepared as described in Example 5 on page 2 of U. S. Patent 2,004,546. Compound 3 above was prepared by replacing the benzidine of Example 3 above by a molecularly equivalent amount of o dianisidine. The 3,3'-di-n-lauryloxacyanine perchlorate can be prepared as described in Jones, Reed and Kuniskis U. S. application S. N. 291,802, filed June 4, 1952.

The Water-soluble compounds of Formulas IX to XII can advantageously be employed in the form of their alkali metal (e. g. sodium, potassium, etc.), ammonium or amine salts, as shown above and in application Serial No. 91,422, mentioned above. In like manner, the compounds of Formulas VI-VIII which contain a sulfo or carboxyl group can be employed in the form of their alkali metal (e. g. sodium, potassium, etc.), ammonium, or amine salts. Such salts are particularly advantageous when it is desired to apply the ultraviolet absorbing compound to the photographic element by a bathing treatment, such as is described above.

What we claim as our invention and desire secured by Letters Patent of the United States is:

v 1. A finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupleddye image subject to fading lying between said support and a gelatin layer containing at least one ultraviolet absorbing compound selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group, X represents an anion, and Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the thiazole series, those of the thiazoline series, and those of the benzothiazole series, and adsorbed to said gelatin outer layer a watersoluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, n represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

2. A finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:

and adsorbed to said gelatin outer layer a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, 11 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons 3. A finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:

cizHzstn) CizHzatn C104 and adsorbed to said gelatin outer layer a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, 12 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

4. A finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:

and adsorbed to said gelatin outer layer a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, 11 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

5. A finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic g'elatino-ernulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:

l (g-CH;

and adsorbed to said gelatin outer layer a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, )1 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

6. A finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:

and adsorbed to said gelatin outer layer a watersoluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, n represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

7. A method of preventing image degradation in a finished photographic element comprising a support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet light absorbing compound selected from those represented by the following formulas:

-COOCH3 (if) n C -CHS l O HOQ-il R wherein R and R1 each represents an alkyl group,- R2 represents amember selected from the group consisting of a hydrogen atom, and alkyl group of l to 3 carbon atoms, and a monocyc'lic aryl group, R3, R4 and Rs each represents a monocyclic aryl group, R5 represents a member selected from the group consisting of an alkyl group and an alkoxyl group, Q represents a member selected from the group consisting of an oxygen atom, a sulfur atom, and an imino group, X represents an anion, Z and Z1 each represents a non-metallic atom necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the thiazole series, those of the thiazoline series, and those of the benzothiazole series, and D represents the non-metallic atoms necessary tocomplete a fluoranthene nucleus, said ultraviolet light absorbing compound affording temporary protection only against the harmful eflects of ultraviolet light due to decomposition on exposure to said ultraviolet light, which comprises bathing said photographic element in an aqueous non-collodial solution of a compound selected from those represented by the following formulas:

N80 38 S O 3N8 wherein D1 represents a monouclear aromatic group of the benzene series, n represents a positive integer of from 1 to 3, and Y represents a member selected from the group consisting of a s-triazinyl group and an acyl group of a i, j, k and I being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

8. A method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:

said ultraviolet light absorbing compound affording temporary protection only against the harmful effects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic elernent in an aqueous non-colloidal solution of a watersoluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, 11 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said sulfonic acid salt being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

9. A method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:

porary protection only against the harmful effects of ul travioIet light due to decomposition on exposure to light,

CODE

QW-QQWQOH which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, n represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboXylic acid, said sulfonic acid salt being absorbent of ultraviolent light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

"'10. A method of preventing image degradation in a finished photographic element comprising a paper supmononuclear aromatic carboxylic acid, said compounds port and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:

said ultraviolet light absorbing compound aifording temporary protection only against the harmful effects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D1 represents a mononuclear aromatic group of the benzene series, n represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxlic acid, said sulfonic acid salt being absorbent of ultraviolent light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

11. A method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:

said ultraviolet light absorbing compound aifording temporary protection only against the harmful effects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D represents a mononuclear aromatic group of the benzene series, 11 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said sulfonic acid salt being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

12. A method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer con- 16 taining an ultraviolet light absorbing compound of the following formula:

said ultraviolet light absorbing compound atfording temporary protection only against the harmful efiects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:

wherein D represents a mononuclear aromatic group of the benzene series, 11 represents a positive integer of from 1 to 2, and Y represents an acyl group of a mononuclear aromatic carboxylic acid, said sulfonic acid salt being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.

13. A finished photographic element comprising a gelatin outer layer and a support having thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupleddye image subject to fading lying between said support and a gelatin layer containing at least one ultraviolet absorbing compound selected from the group consisting of those represented by the following general formulas:

=on-n and wherein R and R1 each represents an alkyl group, R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 3 carbon atoms, and a monocyclic aryl group, R3 R4 and Rs each represents a monocyclic aryl group, R5 represents a member selected from the group consisting of an alkyl group and an alkoxyl group, Q represents a member selected from the group consisting of an oxygen atom, a sulfur atom, and an imino group, X represents an anion, Z and Z1 each represents a non-metallic atom necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the thiazole series, those of the thiazoline series, and those of the benzothiazole series, and D represents the non-metallic atoms necessary to complete a fluoranthene nucleus, and adsorbed to said gelatin outer layer a water-soluble ultraviolet absorbing compound selected from the group consisting of those represented by the following formulas:

SOrNa (J) NaOaB and 20 wherein D1 represents a mononuclear aromatic group of GOOH References Cited in the file of this patent UNITED STATES PATENTS 2,241,239 Carroll et a1. May 6, 1941 2,295,013 Schinzel Sept. 8, 1942 FOREIGN PATENTS 493,308 Great Britain Oct. 6, 1938 565,929 Great Britain Dec. 5, 1944 

7. A METHOD OF PREVENTING IMAGE DEGRADATION IN A FINISHED PHOTOGRAPH ELEMENT COMPRISING A SUPPORT AND SUPERPOSED THEREON A PLURALITY OF DEVELOPED AND FIXED PHOTOGRAPHIC EMULSION LAYERS CONTAINING COUPLED-DYE IMAGES, AT LEAST ONE OF SAID DYE IMAGES BEING SUBJECT TO FADING BY THE ACTION OF ULTRAVIOLET LIGHT, SAID EMULSION LAYER CONTAINING A COUPLED-DYE IMAGE SUBJECT TO FADING LYING BETWEEN SAID SUPPORT AND A GELATIN LAYER CONTAINING AN ULTRAVIOLET LIGHT ABSORBING COMPOUND SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING FORMULAS: 